Density functional theory investigation on the NH3 and CO2 absorption by functional ionic liquids

doi:10.11949/0438-1157.20220603

Abstract

Abstract:

Due to their unique structural tunability, ionic liquids (ILs) can be used as additives to effectively suppress NH₃ escape and simultaneously promote CO₂ uptake in ammonia-based carbon capture. Revealing the absorption mechanism of CO₂ and NH₃ by ILs plays an important role in reconstructing new functional ILs. In this paper, an analysis of five bifunctional ionic liquids based on structure optimization, frequency calculation and atomic charge has been carried out by using density functional theory (DFT) at B3LYP/6-31'++G (d, p) level, and the data of the optimized structures have been achieved. Then, the interaction among ILs, CO₂ and NH₃ has been analyzed. The calculated results demonstrated that [HEBim][His] shows the best stability, of which its interaction energy reaches -415.73 kJ·mol^-1after basis function overlap error correction. The best sites for interaction with NH₃ and CO₂ were found by analyzing the electrostatic potential and charge of the designed ILs: NH₃ mainly forms O—H…N hydrogen bond with the hydroxyl groups of ILs cation, and [HEBim][His] has the strongest ability to absorb NH₃, with a hydrogen bonding energy of 38.52 kJ·mol^-1, which has a strong hydrogen bonding effect; CO₂ mainly forms C—N…C hydrogen bonds with the amino group in the anion, and [HEBim][Ala] has the strongest ability of CO₂ absorption, the formed hydrogen bonding energy of 10.15 kJ·mol^-1, which is a relatively weak hydrogen bonding. When ILs interact with NH₃ and CO₂ at the same time, their absorption capacity decreased to different degrees, and the comprehensive absorption effect of [HEBim][His] and [HEBim][Ala] was the best.

Key words: CO₂ capture, ammonia escape, ionic liquids, density functional theory, hydrogen bond, topological analysis of electron density

摘要：

离子液体（ILs）由于其独特的结构可调性，作为添加剂可有效抑制氨法碳捕集中NH₃的逃逸并同时促进CO₂的吸收。揭示其吸收NH₃和CO₂的作用机理对于构建特定的功能型ILs结构具有重要意义。本文采用密度泛函理论（DFT），在B3LYP/6-31'++G（d，p）基组水平下对设计的五种功能型ILs进行了结构优化、频率计算以及原子电荷分析，获得了优化后的结构参数、振动频率以及原子电荷等数据。在此基础上对ILs吸收CO₂和NH₃进行了相互作用分析。计算结果表明：[HEBim][His]的稳定性最好，经过BSSE校正后的相互作用能为-415.73 kJ·mol^-1。通过静电势和电荷分析找到了设计的ILs与气体作用的最佳位点：NH₃主要与ILs阳离子的羟基形成 O—H…N型氢键，其中，[HEBim][His]吸收NH₃的能力最强，形成的氢键结合能为38.52 kJ·mol^-1，具有较强的氢键作用；CO₂主要与阴离子中的氨基形成C—N…C型氢键，[HEBim][Ala]吸收CO₂的能力最强，形成的氢键结合能为10.15 kJ·mol^-1，具有较弱的氢键作用。当ILs同时与NH₃和CO₂相互作用时，其吸收能力均有不同程度的下降，[HEBim][His]与[HEBim][Ala]的综合吸收效果最佳。

关键词: 碳捕集, 氨逃逸, 离子液体, 密度泛函理论, 氢键, 电子密度拓扑分析

CLC Number:

O 641.2

Xianhui ZHU, Fu WANG, Jiecheng XIA, Jinliang YUAN. Density functional theory investigation on the NH₃ and CO₂ absorption by functional ionic liquids[J]. CIESC Journal, 2022, 73(10): 4324-4334.

朱先会, 王甫, 夏杰成, 袁金良. 功能型离子液体协同吸收NH₃和CO₂的密度泛函理论研究[J]. 化工学报, 2022, 73(10): 4324-4334.

Figures/Tables 13

References 30

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Structure	BCP	ρ_BCP/a.u.	∇²ρ_BCP/a.u.	E_HB/ (kJ·mol^-1)
[HEMim][Glu]	C1—H4—O35	0.04886	0.12196	42.5
[HEMim][Glu]	C10—H12—O35	0.01331	0.03917	9.32
[HEMim][Glu]	C17—H18—O34	0.02293	0.06332	18.33
[HEMim][Asp]	C1—H6—O28	0.04452	0.12057	38.45
[HEMim][Asp]	C9—H11—O29	0.02270	0.06867	18.07
[HEMim][Asp]	C16—H18—O28	0.01305	0.04481	9.04
[HEBim][Asp]	C1—H7—O37	0.05038	0.13735	43.92
[HEBim][Asp]	C11—H13—O38	0.01245	0.04123	8.54
[HEBim][Asp]	O14—H15—O38	0.02940	0.10492	24.35
[HEBim][Ala]	C1—H6—O37	0.04807	0.13029	41.76
[HEBim][Ala]	C22—H23—O38	0.01340	0.04554	9.41
[HEBim][Ala]	O28—H29—O38	0.02945	0.10705	24.39
[HEBim][Ala]	O37—H41—N39	0.01887	0.07515	14.52
[HEBim][His]	C1—H9—O48	0.04721	0.12949	40.96
[HEBim][His]	C11—H13—O47	0.01355	0.04557	9.54
[HEBim][His]	O17—H18—O47	0.03139	0.11223	26.19
[HEBim][His]	N44—H45—O28	0.01809	0.07527	13.77
[HEBim][His]	N44—H46—N36	0.01247	0.04044	8.54

Structure	BCP	ρ_BCP/a.u.	∇²ρ_BCP/a.u.	E_HB/ (kJ·mol^-1)
[HEMim][Glu]	C1—H4—O35	0.04886	0.12196	42.5
[HEMim][Glu]	C10—H12—O35	0.01331	0.03917	9.32
[HEMim][Glu]	C17—H18—O34	0.02293	0.06332	18.33
[HEMim][Asp]	C1—H6—O28	0.04452	0.12057	38.45
[HEMim][Asp]	C9—H11—O29	0.02270	0.06867	18.07
[HEMim][Asp]	C16—H18—O28	0.01305	0.04481	9.04
[HEBim][Asp]	C1—H7—O37	0.05038	0.13735	43.92
[HEBim][Asp]	C11—H13—O38	0.01245	0.04123	8.54
[HEBim][Asp]	O14—H15—O38	0.02940	0.10492	24.35
[HEBim][Ala]	C1—H6—O37	0.04807	0.13029	41.76
[HEBim][Ala]	C22—H23—O38	0.01340	0.04554	9.41
[HEBim][Ala]	O28—H29—O38	0.02945	0.10705	24.39
[HEBim][Ala]	O37—H41—N39	0.01887	0.07515	14.52
[HEBim][His]	C1—H9—O48	0.04721	0.12949	40.96
[HEBim][His]	C11—H13—O47	0.01355	0.04557	9.54
[HEBim][His]	O17—H18—O47	0.03139	0.11223	26.19
[HEBim][His]	N44—H45—O28	0.01809	0.07527	13.77
[HEBim][His]	N44—H46—N36	0.01247	0.04044	8.54

Structure	Atoms	ESP	ADCH	Hirshfeld
[HEMim][Glu]	O13	-0.7015	-0.4896	-0.2236
[HEMim][Glu]	O31	-0.6499	-0.4914	-0.1804
[HEMim][Glu]	O33	-0.5800	-0.5392	-0.2963
[HEMim][Glu]	O34	-0.8291	-0.3179	-0.3635
[HEMim][Glu]	O35	-0.7445	-0.2780	-0.3485
[HEMim][Glu]	N36	-0.8907	-0.5660	-0.2056
[HEMim][Glu]	H4	0.3344	0.1135	0.0522
[HEMim][Glu]	H5	0.2147	0.1688	0.0720
[HEMim][Glu]	H6	0.2078	0.1686	0.0720
[HEMim][Glu]	H14	0.4238	0.3733	0.1634
[HEBim][Ala]	O28	-0.6796	-0.4611	-0.2436
[HEBim][Ala]	O37	-0.7270	-0.5027	-0.3340
[HEBim][Ala]	O38	-0.7921	-0.4611	-0.3255
[HEBim][Ala]	N39	-1.0336	-0.7204	-0.2306
[HEBim][Ala]	H4	0.2228	0.1274	0.0723
[HEBim][Ala]	H5	0.2238	0.1155	0.0697
[HEBim][Ala]	H6	0.2619	0.2064	0.0527
[HEBim][Ala]	H29	0.4241	0.3252	0.1147

Structure	Atoms	ESP	ADCH	Hirshfeld
[HEMim][Glu]	O13	-0.7015	-0.4896	-0.2236
[HEMim][Glu]	O31	-0.6499	-0.4914	-0.1804
[HEMim][Glu]	O33	-0.5800	-0.5392	-0.2963
[HEMim][Glu]	O34	-0.8291	-0.3179	-0.3635
[HEMim][Glu]	O35	-0.7445	-0.2780	-0.3485
[HEMim][Glu]	N36	-0.8907	-0.5660	-0.2056
[HEMim][Glu]	H4	0.3344	0.1135	0.0522
[HEMim][Glu]	H5	0.2147	0.1688	0.0720
[HEMim][Glu]	H6	0.2078	0.1686	0.0720
[HEMim][Glu]	H14	0.4238	0.3733	0.1634
[HEBim][Ala]	O28	-0.6796	-0.4611	-0.2436
[HEBim][Ala]	O37	-0.7270	-0.5027	-0.3340
[HEBim][Ala]	O38	-0.7921	-0.4611	-0.3255
[HEBim][Ala]	N39	-1.0336	-0.7204	-0.2306
[HEBim][Ala]	H4	0.2228	0.1274	0.0723
[HEBim][Ala]	H5	0.2238	0.1155	0.0697
[HEBim][Ala]	H6	0.2619	0.2064	0.0527
[HEBim][Ala]	H29	0.4241	0.3252	0.1147

ILs-gases	BCP	ρ_BCP/a.u.	∇²ρ_BCP/ a.u.	E_HB/(kJ·mol^-1)
[HEMim][Glu]-NH₃	O13—H14—N39	0.0440	0.1054	37.96
[HEMim][Glu]-CO₂	C27—N36—C39	0.0108	0.0350	6.97
[HEMim][Asp]-NH₃	O19—H20—N36	0.0442	0.1044	38.15
[HEMim][Asp]-CO₂	C21—N39—C36	0.0087	0.0290	5.01
[HEBim][Asp]-NH₃	O14—H15—N45	0.0438	0.1043	37.78
[HEBim][Asp]-CO₂	C31—N37—C45	0.0075	0.0255	3.89
[HEBim][Ala]-NH₃	O28—H29—N42	0.0444	0.1045	38.34
[HEBim][Ala]-CO₂	C34—N37—C42	0.0142	0.0439	10.15
[HEBim][His]-NH₃	O17—H18—N49	0.0446	0.1052	38.52
[HEBim][His]-CO₂	C41—N44—C49	0.0126	0.0393	8.65

Density functional theory investigation on the NH₃ and CO₂ absorption by functional ionic liquids

功能型离子液体协同吸收NH₃和CO₂的密度泛函理论研究

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Figures/Tables 13

References 30

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ILs-gases	BCP	Bond length/ Å	ρ_BCP/a.u.	∇²ρ_BCP/a.u.	E_HB/(kJ·mol^-1)
[HEBim][His]-NH₃-CO₂	O17—H18—N48	1.7886	0.0445	0.1034	38.43
[HEBim][His]-NH₃-CO₂	C41—N44—C53	2.9830	0.0112	0.0345	7.35
[HEBim][Ala]-NH₃-CO₂	O28—H29—N42	1.8015	0.0436	0.1027	37.59
[HEBim][Ala]-NH₃-CO₂	C34—N37—C46	2.8661	0.0129	0.0407	8.93

ILs-gases	H-bonds	sign(λ₂)ρ(r)/a.u.
[HEBim][His]-NH₃	O17—H18…N48	-0.0452
[HEBim][His]-CO₂	C41—N44…C53	-0.0092
[HEBim][Ala]-NH₃	O28—H29…N42	-0.0436
[HEBim][Ala]-CO₂	C34—N37…C46	-0.0128

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